CN105593432B - Piloerection shape artificial leather and its manufacturing method - Google Patents

Piloerection shape artificial leather and its manufacturing method Download PDF

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Publication number
CN105593432B
CN105593432B CN201480053776.8A CN201480053776A CN105593432B CN 105593432 B CN105593432 B CN 105593432B CN 201480053776 A CN201480053776 A CN 201480053776A CN 105593432 B CN105593432 B CN 105593432B
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China
Prior art keywords
macromolecular elastomer
piloerection
fibre
artificial leather
solvent
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CN201480053776.8A
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CN105593432A (en
Inventor
芦田哲哉
小河原治
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Kuraray Co Ltd
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Kuraray Co Ltd
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/007—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by mechanical or physical treatments
    • D06N3/0075—Napping, teasing, raising or abrading of the resin coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/007—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/12—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to leather
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0011—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using non-woven fabrics
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D06N3/145—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes two or more layers of polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/18—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials
    • D06N3/183—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with two layers of different macromolecular materials the layers are one next to the other
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2503/00—Polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2211/00—Specially adapted uses
    • D06N2211/12—Decorative or sun protection articles
    • D06N2211/28—Artificial leather
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N2213/00—Others characteristics
    • D06N2213/03—Fibrous web coated on one side with at least two layers of the same polymer type, e.g. two coatings of polyolefin

Abstract

The present invention provides a kind of manufacturing method of piloerection shape artificial leather, this method comprises: preparing the process of fibre plate, the fibre plate contains fiber number 1dtex superfine fibre below and imparts the non-woven fabrics of the first macromolecular elastomer by being impregnated with；The process for forming piloerection face and the one or both sides to fibre plate carry out fluffing processing；Process of the coating containing the resin liquid to given solvent with the second soluble macromolecular elastomer on piloerection face；And the process that the given solvent is coated on the face for be coated with resin liquid.In addition, the present invention provides a kind of piloerection shape artificial leather, it contains fibre plate, the fibre plate is fibre plate obtained from imparting the first macromolecular elastomer to non-woven fabrics as impregnation, the non-woven fabrics is the pseudoconjugant of fiber number 1dtex superfine fibre below, fibre plate has piloerection face made of making superfine fibre fluffing in its one or both sides, and the second macromolecular elastomer adheres to the root of the superfine fibre of fluffing.

Description

Piloerection shape artificial leather and its manufacturing method
Technical field
The present invention relates to the piloerections that the surface raw material as dress material, shoes, furniture, automotive seat, grocery items etc. use Shape artificial leather.In particular to the piloerection shape artificial leather that the pill resistance that pilling is less likely to occur is excellent, the pilling is Refer to the phenomenon that fiber on surface generates small spherical block by the fluffing such as friction and the mutual obvolvent of its piloerection.
Background technique
At present it is known that there is the such piloerection shape formed through fluffing of chamois leather shape artificial leather, Niu Bage shape artificial leather artificial Leather.
For example, following patent documents 1 disclose the Niu Bage shape people that manufacture has fine and close piloerection sense and fine fold sense The method of fabricate-leather.Specifically, disclosing a kind of manufacturing method of Niu Bage shape artificial leather, this method includes successively carrying out down It states process: being finish-machined to artificial leather matrix made of macromolecular elastomer is contained in the inside of superfine fibre obvolvent non-woven fabrics When piloerection shape artificial leather, the work of the solvent of macromolecular elastomer swelling or dissolution can be made in the coated on one side of artificial leather matrix Sequence；At least one side is subjected to fluffing processing, the process for forming piloerection face；The process that the hair side that opposes assigns macromolecular elastomer；It will The process for imparting the face further progress fluffing processing of macromolecular elastomer.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2007-262616 bulletin
Summary of the invention
Problems to be solved by the invention
In existing piloerection shape artificial leather, it is easy to produce pilling.Pilling there are problems that reducing appearance.The present invention Be designed to provide a kind of piloerection shape artificial leather that pill resistance is excellent.
The method used for solving the problem
An aspect of of the present present invention is a kind of manufacturing method of piloerection shape artificial leather, this method comprises: preparing the work of fibre plate Sequence, the fibre plate contain fiber number 1dtex superfine fibre below and impart the first macromolecular elastomer by impregnation Non-woven fabrics；The process for forming piloerection face and the one or both sides to fibre plate carry out fluffing processing；It is coated on piloerection face Process containing the resin liquid to given solvent with the second soluble macromolecular elastomer；It is being coated with resin liquid The process of solvent given herein above is coated on face.
In addition, another aspect of the present invention is a kind of piloerection shape artificial leather, containing fibre plate, the fibre plate is logical It crosses impregnation and fibre plate obtained from the first macromolecular elastomer is imparted to non-woven fabrics, the non-woven fabrics is fiber number 1dtex or less Superfine fibre pseudoconjugant, fibre plate its one or both sides have so that the superfine fibre is fluffed made of piloerection face, also With cementation fluffing superfine fibre root and be non-uniformly distributed in fibre plate surface layer the second macromolecular elastomer. The pill resistance of such piloerection shape artificial leather is excellent.
The effect of invention
In accordance with the invention it is possible to obtain the higher piloerection shape artificial leather of pill resistance.
Detailed description of the invention
Fig. 1 is the schematic diagram of the section of the thickness direction of the piloerection shape artificial leather of an embodiment of the invention.
Fig. 2 is the SEM photograph of the section of the thickness direction near the surface layer of piloerection shape artificial leather obtained in embodiment 1.
Description of symbols
1a superfine fibre
1 non-woven fabrics
2 first macromolecular elastomers
3 second macromolecular elastomers
10 piloerection shape artificial leathers
S piloerection face
Specific embodiment
Firstly, being illustrated referring to an embodiment of the attached drawing to piloerection shape artificial leather of the invention.Fig. 1 is this reality Apply the schematic diagram of the section of the thickness direction of the piloerection shape artificial leather 10 of mode.
As shown in the constructed profile of Fig. 1, piloerection shape artificial leather 10 have it is for example being formed using fiber bundle-like, as fibre Spend the non-woven fabrics 1 of the pseudoconjugant of 1dtex superfine fibre 1a below.Is imparted in the internal voids of the internal layer of non-woven fabrics 1 One macromolecular elastomer 2.First macromolecular elastomer 2 assigns sense of fulfillment to non-woven fabrics 1.In addition, having on the surface of non-woven fabrics 1 There is the piloerection face S in the presence of superfine fibre 1a made of fluffing.Moreover, the superfine fibre of piloerection root cementation have it is second high Molecular flexibility body 3.
Then an example of the manufacturing method is described in detail the piloerection shape artificial leather of present embodiment.
The piloerection shape artificial leather of present embodiment can be manufactured by the following method and obtain, and the manufacturing method includes: Prepare the process of fibre plate, the fibre plate contains fiber number 1dtex superfine fibre below and imparts first by impregnation The non-woven fabrics of macromolecular elastomer；The process for forming piloerection face and the one or both sides of fibre plate are carried out fluffing processing； Process of the coating containing the resin liquid to given solvent with the second soluble macromolecular elastomer on piloerection face；? It is coated with the process that solvent given herein above is coated on the face of resin liquid.
In the manufacturing method of the piloerection shape artificial leather of present embodiment, firstly, by impregnation to as fiber number 1dtex The non-woven fabrics of the pseudoconjugant of superfine fibre below assigns the first macromolecular elastomer and manufactures fibre plate.
In the manufacture of non-woven fabrics, firstly, the web of fiber type occurs for manufacture superfine fibre.System as web Method is made, can be enumerated for example: fiber type being occurred into for superfine fibre and carries out melt spinning, not by its intentional interruption with long fine The method of the state trapping of dimension；Cut into the method that staple fiber implements well known obvolvent processing later.It should be noted that long Fiber refers to the fiber for not carrying out cutoff process.As long stapled length, from the viewpoint that can fully improve fibre density Consider, preferably for example, 100mm or more, further preferably 200mm or more.The long stapled upper limit is not particularly limited, can be with It is number m, hundreds of m, number km or its longer fibre length made of continuously spinning.Wherein, from fiber is less likely to occur From the viewpoint of decoherencing, the excellent piloerection shape artificial leather of pill resistance capable of being obtained, superfine fibre generation type is particularly preferably manufactured The long fibre net of fiber.In the present embodiment, as representative examples, the long fibre net of fiber type manufacture superfine fibre occurs The case where be described in detail.
Refer to it should be noted that fiber type occurs for superfine fibre by chemically locating afterwards to the fiber implementation after spinning Reason or physical post-processing and form the fiber of the lesser superfine fibre of fiber number.It is sub as its concrete example, it can enumerate for example: In fibre profile, as be dispersed in the sea component polymer of matrix as with the different types of microcell of sea component polymer Island component polymer, the pole of the fiber bundle-like based on the polymer with island component is formed and removing sea component later The islands-in-sea bicomponent fibre of fine fibre；Fiber periphery alternately configure a variety of different resin components and formed petal shape, Overlapping shapes remove each resin component using physical treatment, are thus divided and are formed the removing point of the superfine fibre of pencil Cut type composite fibre etc..According to islands-in-sea bicomponent fibre, in the obvolvent processing for carrying out back narration, can inhibit cracking, The fibre damages such as fracture, cut off.In the present embodiment, as representative examples, to using islands-in-sea bicomponent fibre to form superfine fibre The case where dimension, is described in detail.
Islands-in-sea bicomponent fibre is the multicomponent system composite fibre being at least made of 2 kinds of polymer, is had by sea component The section of island component polymer is dispersed in the matrix that polymer is constituted.The long fibre net of islands-in-sea bicomponent fibre is to island Type composite fibre progress melt spinning, and do not cut off and be captured in long stapled state online and formation.
As long as island component polymer is capable of forming the polymer of superfine fibre, it is not particularly limited.It is specific and Speech, can enumerate for example: polyethylene terephthalate (PET), gathers to benzene two at polypropylene terephthalate (PTT) The polyester resins such as formic acid butanediol ester (PBT), polyester elastomer or their modifier by M-phthalic acid etc.；Polyamides Amine 6, polyamide 66, polyamide 610, polyamide 12, aromatic polyamide, semiaromatic polyamide composition, polyamide elastomer etc. are poly- Amide resinoid or their modifier；The polyolefin resins such as polypropylene；Polyurethane based resins such as polyester-based polyurethane etc.. Wherein, since PET, PTT, PBT, their polyester resins such as modified poly ester are easy through heat treatment contraction, energy The piloerection shape artificial leather with sense of fulfillment is accessed, is considered from the viewpoint, preferably these resins.In addition, polyamide 6, polyamide 66 equal polyamide-based resins have hygroscopicity compared with polyester resin, can obtain submissive superfine long fibre, therefore can The piloerection shape artificial leather of the soft feel with inflated sense is obtained, is considered from the viewpoint, preferably these resins.
As sea component polymer, it can choose and compare the dissolubility of solvent with island component polymer phase or utilize decomposition The higher polymer of the decomposability of agent.In addition, from the stability of spinning process of islands-in-sea bicomponent fibre it is excellent from the viewpoint of, preferably It is smaller with the compatibility of island component polymer and melt viscosity and/or surface tension are less than island component and polymerize under spinning condition The polymer of object.As the specific example for the sea component polymer for meeting such condition, can enumerate for example: water-soluble poly Vinyl alcohol resin (water-solubility PVA), polyethylene, polypropylene, polystyrene, ethylene-propylene analog copolymer, ethylene-acetate second Enester analog copolymer, styrene-ethylene analog copolymer, styrene acrylic copolymers etc..Wherein, due to water-solubility PVA Aqueous medium dissolution can be utilized to remove without using organic solvent, thus from environmental pressure it is lower from the viewpoint of, preferred water Dissolubility PVA.
Islands-in-sea bicomponent fibre can by by sea component polymer and island component polymer from composite spinning nozzle into The melt spinning of row melting extrusion manufactures.As long as the nozzle temperature of composite spinning nozzle is than sea component polymer and island The high temperature for being able to carry out melt spinning of the fusing point of the two of component polymer, is not particularly limited, generally selects 180~350 DEG C of range.
The fiber number of islands-in-sea bicomponent fibre is not particularly limited, preferably 0.5~10dtex, further preferably 0.7~ 5dtex.In addition, the average area of sea component polymer on the section of islands-in-sea bicomponent fibre and island component polymer is than excellent It is selected as 5/95~70/30, further preferably 10/90~50/50.In addition, the island component on the section of islands-in-sea bicomponent fibre Microcell quantity be not particularly limited, but from the viewpoint of industrial productivity, preferably 5~1000, further preferably 10~300 or so.
The islands-in-sea bicomponent fibre of the molten condition sprayed from nozzle is cooled by cooling device, recycles jet The suction units such as nozzle carry out traction refinement with the high-speed flow for being equivalent to 1000~6000m/ minutes pumping velocities, make it Fiber number as target.And the long fibre by obtaining traction refinement is deposited in the collection faces such as mobile net, can be obtained To long fibre net.It should be noted that as needed, it, can be by the way that long fibre net be further added in order to make form stable It presses and crimps it partly.The weight per unit area of the long fibre net obtained in this way is not particularly limited, such as preferably 10 ~1000g/m2Range.
Then, obvolvent net is manufactured and implementing obvolvent processing to obtained long fibre net.
The specific example that obvolvent as long fibre net is handled, can enumerate long fibre such as using cloth folding device Net is in thickness direction overlying multiple layers, then in the item for the hook (harb) for simultaneously or alternately running through at least one or more from its two sides The processing of needle thorn is carried out under part.
In addition, for long fibre net, any one rank for being handled from the spinning process of islands-in-sea bicomponent fibre to obvolvent Duan Zhongjun can assign finish, antistatic agent.Moreover, by carrying out for long fibre net being impregnated in 70~150 DEG C of left sides as needed The shrink process of right warm water can make the obvolvent state of long fibre net become fine and close in advance.In addition, by after needling Hot-pressing processing is carried out, fibre density can further be made to become fine and close and assign morphological stability.As the obvolvent obtained in this way The weight per unit area of net, preferably 100~2000g/m2The range of left and right.
Furthermore it is also possible to implement to improve fibre density and obvolvent journey by being as needed heat-shrinked obvolvent net The processing of degree.As the specific example for being heat-shrinked processing, the method for contacting obvolvent net with vapor, right can be enumerated for example Obvolvent net passes through the side that the heating electromagnetic waves such as air or infrared ray heat the water for imparting obvolvent net after assigning water Method.In addition, hot-pressing processing can be carried out as needed.By carrying out hot-pressing processing, can make to be caused by being heat-shrinked processing The obvolvent net of densification further densifies, while can make the form immobilization of obvolvent net, makes surface smoothing.
The variation of weight per unit area as the obvolvent net being heat-shrinked in treatment process, with the unit before shrink process Area weight is compared, preferably 1.1 times (mass ratio) or more, further preferably 1.3 times or more, preferably 2 times hereinafter, into One step is preferably 1.6 times or less.
Moreover, as removing sea component polymerization in the islands-in-sea bicomponent fibre in the obvolvent net obtained from densified Object can obtain the superfine long stapled non-woven fabrics of the superfine long stapled pseudoconjugant as fiber bundle-like.As from fabric of island-in-sea type The method that sea component polymer is removed in composite fibre can be not particularly limited only selectively remove using utilization Remove the solvent of sea component polymer or method that distintegrant handles obvolvent net.Specifically, for example using water-soluble , it is preferable to use hot water is as solvent in the case that PVA is as sea component polymer.In addition, in the modification using easy caustic digestion Polyester as sea component polymer in the case where it is preferable to use the alkaline decompositions agent such as sodium hydrate aqueous solution.
In the case where using water-solubility PVA as sea component polymer, preferably by 85~100 DEG C of hot water It is removed to extract within processing 100~600 seconds, so that the removal rate of water-solubility PVA is 95~100 mass % or so.It needs Illustrate, applies dipping clamping processing by repeating, removing water-solubility PVA can be efficiently extracted.Using water-soluble In the case where PVA, sea component polymer is selectively removed since organic solvent can not used, from environmental pressure It is lower and be able to suppress from the viewpoint of the generation of VOC, preferred water-solubility PVA.
The fiber number of the superfine fibre formed as described above is 1dtex hereinafter, preferably 0.001~1dtex, further excellent It is selected as 0.002~0.2dtex.
The weight per unit area of the superfine long stapled non-woven fabrics obtained in this way is preferably 140~3000g/m2, further Preferably 200~2000g/m2.In addition, obtaining the sight of the non-woven fabrics with sense of fulfillment from by forming fine and close non-woven fabrics Point considers that the apparent density of preferably superfine long stapled non-woven fabrics is 0.45g/cm3More than, further preferably 0.55g/cm3With On.The upper limit is not particularly limited, from can obtain submissive feel and productivity it is excellent from the viewpoint of, preferably 0.70g/ cm3Below.
In the manufacture of the piloerection shape artificial leather of present embodiment, the superfine fibre as by islands-in-sea bicomponent fibre The front and back that fiber type carries out superfine fibre occurs, assigns the to the internal voids of superfine long stapled non-woven fabrics by being impregnated with One macromolecular elastomer.First macromolecular elastomer assigns morphological stability, sense of fulfillment to non-woven fabrics.
It as the specific example of the first macromolecular elastomer, can enumerate for example: polyurethane, acrylic resin elasticity Body, vinyl cyanide resin-elastomer, olefine kind resin elastomer, polyester resin elastomer etc..As the first high polymer elastic Body is, it is preferable to use to the lower high score bullet of the dissolubility of the solvent for dissolving the second macromolecular elastomer described below Property body, and can be used due to forming cross-linked structure after solidification and to the lower high score bullet of the dissolubility of above-mentioned solvent Property body.To the lower macromolecular elastomer of the dissolubility of above-mentioned solvent, it is preferable to use formed after solidification as such The aqueous polyurethane of cross-linked structure.
Aqueous polyurethane refers to by polyaminoester emulsion or is scattered in the polyurethane dispersing liquid of aqueous solvent and solidifies Polyurethane, usually to organic solvent have insoluble or slightly solubility, be after solidification formed cross-linked structure polyurethane.Separately Outside, in the case where lotion has heat-sensitive gel, emulsion particle does not occur to migrate and carry out heat-sensitive gel, therefore energy It is enough equably to assign the first macromolecular elastomer to fiber pseudoconjugant.
As the method for assigning the first macromolecular elastomer to non-woven fabrics by impregnation, can enumerate: to superfine fibre Lotion of the non-woven fabrics impregnation containing the first macromolecular elastomer, dispersion liquid or solution after preceding obvolvent net or superfine fibre, Then the dry method of solidification is made it dry；Or make the method etc. of its solidification using wet process.It should be noted that solidifying having used It, can basis in order to promote to be crosslinked in the case where forming macromolecular elastomer as the aqueous polyurethane of cross-linked structure after Gu Need to implement the maturation process heated after solidification and drying.
It as the impregnation method of the lotion of the first macromolecular elastomer, dispersion liquid or solution etc., can enumerate: carry out 1 time Or the processing repeatedly squeezed in a manner of reaching given impregnated state with pressure roller etc. dipping chucking method, stick coating method, scrape Knife rubbing method, rolling method, unfilled corner wheel rubbing method (comma coating), spray coating method etc..
It should be noted that within the scope of the effect of the invention, the first macromolecular elastomer can also contain The colorants such as dyestuff, pigment, coagulation regulator, antioxidant, ultraviolet absorbing agent, fluorescer, mould inhibitor, bleeding agent, defoaming Agent, lubricant, waterproofing agent, oil-proofing agent, tackifier, incremental agent, curing accelerator, foaming agent, polyvinyl alcohol, carboxymethyl cellulose The water-soluble high-molecular compounds such as element, inorganic particles, conductive agent etc..
From the viewpoint of the balancing good of the sense of fulfillment of obtained piloerection shape artificial leather and submissive sense etc., as first The content ratio of macromolecular elastomer, the quality preferably with respect to superfine fibre are 0.1~60 mass %, further preferably 0.5~60 mass %, particularly preferably 1~50 mass %.
Fibre plate available in this way, the fibre plate are that the first macromolecular elastomer and fibre are imparted by impregnation Spend the non-woven fabrics of 1dtex superfine fibre below.The fibre plate obtained in this way is as desired by vertical with thickness direction Direction is sliced into multiple and is ground and carries out thickness adjusting, then using polishing papers such as sand paper, emery papers at least Grinding process is carried out on one side, thus implements fluffing processing.As the model of polishing paper, preferably 120~800 models, further Preferably 320~600 models or so.The one or both sides of fibre plate fluffing processing has been subjected to as set forth above, it is possible to be formed Piloerection face.
The thickness of the fibre plate handled through fluffing is not particularly limited, preferably 0.2~4mm, further preferably 0.5~2.5mm.
Then, coating contains to given solvent with solubility on the piloerection face of the fibre plate obtained as described above Then the resin liquid of second macromolecular elastomer solidifies the second macromolecular elastomer.
The second macromolecular elastomer for being dissolved in given solvent is after being dissolved in a subsequent process step with given solvent from molten The macromolecular elastomer of the state solidification of solution.As the second macromolecular elastomer, as long as having to given organic solvent can The macromolecular elastomer of dissolubility can be not particularly limited using.
It as the specific example of the second macromolecular elastomer, can enumerate for example: have to given organic solvent solvable Polyurethane, the acrylic resin elastomer, vinyl cyanide resin-elastomer, olefine kind resin elastomer, polyester resin of property Elastomer etc..As the second macromolecular elastomer, can be used has soluble high polymer elastic to given organic solvent Body can also use and not form cross-linked structure after solidification and have soluble macromolecule to organic solvent given herein above Elastomer.Have soluble macromolecular elastomer, it is preferable to use after solidification organic solvent given herein above as this The solvent system polyurethane of cross-linked structure is not formed.
Solvent system polyurethane refer to organic solvent have it is soluble, make polymer diol, diisocyanate and have Poly- ammonia obtained from least one kind of low molecular compound of 2 or more reactive hydrogen atoms is reacted with given molar ratio Ester, the polymer diol are selected from such as polyester-diol of average molecular weight 500~3000, polyetherdiol, polycarbonate glycol At least one kind of in, the diisocyanate is selected from 4,4 '-methyl diphenylene diisocyanates, isophorone diisocyanate It is at least one kind of in the aromatics such as ester, hexamethylene diisocyanate, the alicyclic ring same clan, aliphatic category diisocyanate etc..It is poly- Urethane can according to need to be used as the polymer composition added with polymer such as synthetic rubber, polyester elastomers.With The aqueous polyurethane of cross-linked structure to be formed is compared, the film of solvent system polyurethane high elongation rate easy to form.
It should be noted that for the solubility to given solvent, such as preferably have 100 μm of thickness of height The sheet material of molecular flexibility body impregnates 24 hours in given solvent under room temperature, then filter solvents, by obtained residue into Row is dry and measures its quality, finds out dissolution rate using following formula, and preferably the dissolution rate is 70% or more, further preferably 90% or more dissolubility.It on the other hand, is 30% hereinafter, further excellent to the insoluble preferred dissolution rate of given solvent It is selected as 10% or less.
Dissolution rate (%)=(weight of 1- residue/solvent impregnated preceding sheet material weight) × 100
As the method for being coated with the resin liquid containing the second macromolecular elastomer on the piloerection face of fibre plate, Ke Yilie It lifts: gravure coating process, stick coating method, scraper for coating method, rolling method, unfilled corner wheel rubbing method, spray coating method etc..
By being coated with the resin liquid containing the second macromolecular elastomer on the piloerection face of fibre plate and making it as needed Dry solidification, can the piloerection face to fibre plate assign the second macromolecular elastomer.
Within the scope of the effect of the invention, the second macromolecular elastomer can also further contain dyestuff, face Colorants, coagulation regulator, antioxidant, ultraviolet absorbing agent, fluorescer, mould inhibitor, bleeding agent, defoaming agent, the lubrications such as material Agent, waterproofing agent, oil-proofing agent, tackifier, incremental agent, curing accelerator, foaming agent, polyvinyl alcohol, carboxymethyl cellulose etc. are water-soluble Property high-molecular compound, inorganic particles, conductive agent etc..
From the sense of fulfillment of obtained piloerection shape artificial leather and it is submissive sense etc. balancing good viewpoint and suitably fetter From the viewpoint of the fiber of hair, as the content ratio of the second macromolecular elastomer, the quality preferably with respect to fibre plate is 0.00001~0.01 mass %, further preferably 0.0001~0.001 mass %.In containing for the second macromolecular elastomer In the case that ratio is excessively high, there are surfaces to be hardened, is easy to produce the tendency of thin gauffer.
It should be noted that from the viewpoint of the balancing good of the sense of fulfillment of piloerection shape artificial leather and submissive sense etc. and appropriate From the viewpoint of the fiber of ground constraint fluffing, preferably the weight per unit area of the second macromolecular elastomer is high for above-mentioned first 0.0001~0.1 times of the weight per unit area of molecular flexibility body, further preferably 0.001~0.05 times.
Then, the solvent that coating dissolves the second macromolecular elastomer on the face for being coated with the second macromolecular elastomer. Process in this way can make to assign at least part dissolution of the second macromolecular elastomer in the piloerection face of fibre plate And penetrate into internal layer direction and dry solidification.Therefore, the second macromolecular elastomer adhere to fluff present on piloerection face it is superfine The root of fiber.The root of the superfine fibre of particularly preferred second macromolecular elastomer cementation piloerection, and in the piloerection of fibre plate The surface layer in face exists with relatively thin membranaceous or stratiform.Therefore, as described above, existing by being fettered with the second macromolecular elastomer In the root of the superfine fibre in piloerection face, even if friction piloerection face, superfine fibre are also not easy to decoherence, it is not easy to make superfine fibre Dimension projects to outside from inside.As a result, the fiber to fall off or outstanding for being able to suppress the friction due to surface and occurring Fiber forms pilling effect as ball top.
The method for the solvent that coating dissolves the second macromolecular elastomer on the face for being coated with the second macromolecular elastomer Be not particularly limited, can enumerate for example: gravure coating process, stick coating method, scraper for coating method, rolling method, unfilled corner wheel coating process, Spray coating method etc..
As the solvent for dissolving the second macromolecular elastomer, dissolvable second is high as long as with coating is only passed through The deliquescent solvent of molecular flexibility body can be not particularly limited using.Such solvent can be according to the second high score The type of elastic body and suitably select.It is sub as its concrete example, such as in the case where dissolving solvent system polyurethane, it can To enumerate: the ketones such as cyclohexanone, methyl ethyl ketone (MEK), N,N-dimethylformamide (DMF), dimethyl acetamide (DMA), N-Methyl pyrrolidone, dimethyl sulfonamide (DMSO) etc..These substances are mixed with given ratio in addition, both can be used Mixed solvent made of conjunction can also mix the poor solvent of the first macromolecular elastomer.
The coating weight for dissolving the solvent of the second macromolecular elastomer can balance according to desired feel, characteristic, thickness Deng and appropriate adjustment, such as preferably with become 1~50g/m2, further preferably 5~30g/m2The mode of left and right is coated. In the case where the coating weight of solvent is excessive, inclining for internal layer is excessively infiltrated into there are the second macromolecular elastomer excessive dissolution To.In addition, since the second macromolecular elastomer does not dissolve fully, existing in the case where coating weight is very few and being difficult to fill Divide the tendency of the root of the superfine fibre of ground cementation fluffing.
In addition, in the piloerection shape artificial leather of present embodiment, for example, preferably second is high as shown in the SEM photograph of Fig. 2 Molecular flexibility body 3 is permeated in fibre plate, the root of the superfine fibre 1a of cementation piloerection, and the table of the piloerection face 1a in fibre plate Layer unevenly exists with relatively thin membranaceous or stratiform.From the viewpoint of it can obtain submissive piloerection shape artificial leather, as With the average thickness of part existing for the second macromolecular elastomer in the presence of relatively thin membranaceous or stratiform, preferably 5~60 μ M, further preferably 10~40 μm.In the case that the part existing for the second macromolecular elastomer is blocked up, there are surface section changes Firmly, the tendency of thin gauffer is easy to produce on surface.In addition, the situation that the part existing for the second macromolecular elastomer is excessively thin Under, it is reduced there are the effect of the superfine fibre of the second macromolecular elastomer cementation piloerection and reduces the effect for inhibiting pilling Tendency.
In addition, in the piloerection shape artificial leather of present embodiment, relative to the thickness of fibre plate, as the second macromolecule The average proportions of the thickness of part existing for elastomer, preferably 1~20%, further preferably 5~10%.It is high second The thickness of part existing for molecular flexibility body relative to the ratio of the thickness of fibre plate it is excessively high in the case where, there are fibre plate at For the tendency of harder feel.
The piloerection shape artificial leather of available present embodiment as described above.The piloerection shape artificial leather of present embodiment The length of the fiber of fluffing is not particularly limited, from can obtain undercoat sense superfine as natural Niu Bage shape leather From the viewpoint of excellent piloerection shape artificial leather, preferably 1~500 μm, further preferably 30~200 μm.It needs to illustrate It is that the length of the fiber of fluffing can obtain in the following manner: for example, making the vertical of the surface of piloerection shape artificial leather with hand Hair shoots cross sectional photograph in the state of hold up, using scanning electron microscope (SEM), to arbitrary 50 from conduct The length of obvolvent surface to the upper end of pilomotor fibers of its root measures, and calculates its average value, thus fluffed The length of fiber.
In addition, the piloerection shape of preferably present embodiment is artificial from the viewpoint of the balancing good of submissive sense and sense of fulfillment The apparent density of leather is 0.4~0.7g/cm3, further preferably 0.5~0.6g/cm3.Moreover, from submissive sense and sense of fulfillment From the viewpoint of balancing good, preferably the weight per unit area of the piloerection shape artificial leather of present embodiment is 150~1000g/ m2, further preferably 200~600g/m2。
It should be noted that the piloerection shape artificial leather of present embodiment can according to need and be dyed.Dyestuff can root It is suitably selected according to the type of superfine fibre.For example, preferably using and dividing in the case where forming superfine fibre by polyester resin Scattered dyestuff is dyed.It as the specific example of disperse dyes, can enumerate for example: benzeneazo class dyestuff (monoazo, double idols Nitrogen etc.), (thiazolylazo, benzothiazole azo, quinoline azo, pyridylazo, imidazoles azo, thiophene are even for heterocycle azo class dyestuff Nitrogen etc.), anthraquinone dyes, condensation class dyestuff (quinophthalone, styryl, cumarin etc.) etc..These substances as example with The dyestuff of the prefix of " Disperse " and it is commercially available.These substances can be used alone, can also combine 2 kinds it is used above.Separately Outside, as colouring method, can be not particularly limited using using high pressure liquid stream decoration method, dye gigging (jigger) decoration method, The decoration method of thermosol continuous dyeing machine method, sublimation printing mode etc..
In addition, in order to further adjust feel, can the piloerection shape artificial leather to present embodiment implement kneading softness Processing, the bristle processing of loose processing and the inverse sealing of implementation, antifouling process, hydrophilicity-imparting treatment, lubricant processing, softening agent The finishing processing such as processing, antioxidant processing, ultraviolet absorbing agent processing, fluorescer processing, fire retardant processing.
Since the pilomotor fibers temporarily to fluff to be adhered to the surface of fibre plate using the second macromolecular elastomer, Even if being dyed, loose processing, it is also difficult to extract pilomotor fibers.
As described above, by being adjusted, so that root is present in piloerection by the superfine fibre that macromolecular elastomer fetters Face, the piloerection shape artificial leather of available present embodiment.Even if such piloerection shape artificial leather opposition hair side rubs, Also it is able to suppress the fiber to fall off, fiber outstanding forms pilling effect as ball top.
Embodiment
Hereinafter, the present invention is further concretely demonstrated by embodiment.It should be noted that model of the invention Enclose any restriction not by embodiment.
[embodiment 1]
Ethylene modified polyvinyl alcohol, the thermoplastic resin as island component for making the thermoplastic resin as sea component The PET of isophthalate modified is separately melted.It should be noted that the ethylene unit of ethylene modified polyvinyl alcohol Content ratio is 8.5 moles of %, the degree of polymerization 380, saponification degree are 98.7 moles of %.In addition, the PET of isophthalate modified Isophthalic acid units content ratio be 6.0 moles of %, fusing point is 110 DEG C.Then, each molten resin is supplied in multiple Spinning nozzle is closed, the composite spinning nozzle is configured with multiple nozzle bores with simultaneously column-shaped, can be formed and be divided in sea component It is furnished with the section of the island component of 25 uniform cross-sections product.At this moment, it carries out pressure adjustment and supplies, so that the melting tree of sea component The mass ratio of the molten resin of rouge and island component is sea component/island component=25/75.Then, by being set as nozzle temperature 260 DEG C of nozzle bore sprays the resin streak with the melting of section of island structure.
Then, it is aspirated and is drawn with resin streak of the suction unit of jet nozzle type to the melting sprayed by nozzle bore It stretches, is spun to the fabric of island-in-sea type composite long fiber that fiber number is 2.1dtex, the pressure of the suction unit of the jet nozzle type to air-flow Power is adjusted, so that average spinning speed is 3700m/ points.For the fabric of island-in-sea type composite long fiber that spinning obtains, on one side It is aspirated from the back side of net, is continuously deposited in the online of movable type on one side.Accumulating amount can be by adjusting the movement speed netted It adjusts.Then, it in order to inhibit the fluffing on surface, is gently pressed with 42 DEG C of metallic rolls and is piled up in online fabric of island-in-sea type composite long fiber. Then, fabric of island-in-sea type composite long fiber is removed from network, makes it between 75 DEG C of surface temperature of check metallic roll and back flow roll Pass through, has thus carried out hot pressing under pressure 200N/mm online.As set forth above, it is possible to which the fiber for obtaining surface is temporarily fused into grid The weight per unit area 34g/m of shape2Long fibre net.
Then, the finish of antistatic agent is mixed in the surface spray imparting of obtained long fibre net.Then, using folded 10 long fibre nets are overlapped by cloth apparatus, and making total weight per unit area is 340g/m2Overlay network, then spraying anti-broken needle oil Agent.Moreover, carrying out three-dimensional obvolvent processing and carrying out needle thorn to the long fibre net of overlapping.Specifically, using from needle tip To the 1st hook distance be 3.2mm the needle with 6 hooks, with the needle depth of 8.3mm from the two sides of laminated body alternately with 3300 thorns/cm2Carry out needle thorn.Percentage reduction of area caused by the needling treatment is 18%, the unit area of the obvolvent net after needle thorn Weight is 415g/m2。
Obtained obvolvent Netcom, which is crossed, to carry out damp and hot shrink process and densifies.Specifically, with relative to obvolvent net be 10 The mode of the ratio of quality % is equably sprayed 18 DEG C of water, temperature 70 C, relative humidity 95% atmosphere in not The state for applying tension is placed 3 minutes and is heat-treated, and is thus carried out damp and hot contraction and is improved fibre density.The damp and hot receipts Percentage reduction of area caused by contracting is handled is 45%, and the weight per unit area of the obvolvent net after densification is 750g/m2, apparent close Degree is 0.52g/cm3.Then, in order to densify obvolvent net further, apparent density is adjusted to by carrying out xeothermic roll-in 0.60g/cm3。
Then, the lotion of the solid component concentration 30% of the first macromolecular elastomer is impregnated with to the obvolvent net after densification. It should be noted that the first macromolecular elastomer is aqueous polyurethane, the aqueous polyurethane forms crosslinking knot after solidification Structure, and with the dissolution rate to the mixed solvent described below be 5% polycarbonate below/ethers polyurethane based on.So Afterwards, by the way that the lotion of the first macromolecular elastomer of impregnation is dried in 150 DEG C of drying oven, make aqueous polyurethane It is solidified in obvolvent net after densification.
Then, it is removed by impregnating to extract for 20 minutes the obvolvent net for imparting aqueous polyurethane in 95 DEG C of hot water Remove sea component contained by fabric of island-in-sea type composite long fiber.Then, by being dried in 120 DEG C of drying oven, available tax The fibre plate of the superfine long stapled non-woven fabrics containing fiber number 0.08dtex of aqueous polyurethane is given.Nonwoven in fibre plate Cloth/aqueous polyurethane mass ratio is 87/13.Then, fibre plate is sliced in thickness direction and is divided into 2 parts, with 600 The sand paper of model polishes to surface, to carry out fluffing processing.
Then, the molten of the mixed solvent for being substantially dissolved completely in DMF 5% and cyclohexanone 95% is prepared as described below The solution of agent system polyurethane is as the solution containing the second macromolecular elastomer.
By the polyhexamethylene carbonic ester of 260 mass parts of polyester-diol of number-average molecular weight 2000, number-average molecular weight 2000 The polytetramethylene of 620 mass parts, 580 mass parts of polybutene adipate ester of number-average molecular weight 2000, number-average molecular weight 2000 540 mass parts of glycol, 217 mass parts of ethylene glycol, 1149 mass parts of diphenyl methane -4,4 '-diisocyanate and DMF 10100 mass parts are put into reactor, are reacted under nitrogen flowing, and the polyurethane solutions of weight average molecular weight 360,000 are made.It needs It is noted that it is N methyldiethanol amine and 3- methyl-1,5- penta that the polyester-diol of number-average molecular weight 2000, which is diol component, The mixture of the equimolar amounts of glycol, dicarboxylic acid component are decanedioic acid.
Then, solid component 5% is prepared into so that cyclohexanone to be added in polyurethane solution.Then, recessed using 200 purposes Version coating machine is with 11g/m2Ratio applying solid ingredient 5% on the surface in the piloerection face of fibre plate polyurethane solutions, so After be dried.At this moment, relative to the aqueous polyurethane previously assigned, the ratio of the weight per unit area of solvent system polyurethane (solvent system/water system) is 0.012 times.
Then, using the gravure coater of 200 mesh with 10g/m2Ratio be coated on the surface in the piloerection face of non-woven fabrics The DMF 5% of dissolution solvent system polyurethane and the mixed solvent of cyclohexanone 95%, are then dried.
Then, by piloerection shape artificial leather in 80 DEG C of hot water Hot water immersion 20 minutes, make its merged with hot water and pine It speeds, is then coloured to black using high pressure liquid stream overflow dyeing machine (the dyeing cycle machine of day slope production Co., Ltd., institute).
As described above, having obtained the superfine long stapled non-woven fabrics containing fiber number 0.08dtex, and there is piloerection in one side Piloerection shape artificial leather after the dyeing in face.Fig. 2 shows cuing open for the thickness direction of piloerection shape artificial leather obtained in embodiment 1 The SEM photograph in face.Obtained piloerection shape artificial leather is thickness 0.6mm, weight per unit area 350g/m2, apparent density 0.58g/ cm3.In addition, the length of the fiber of fluffing is about 80 μm or so.Moreover, the infiltration of the second macromolecular elastomer is in fibre plate and glues It is fixed in the root of the superfine fibre of piloerection, the surface layer of fibre plate is unevenly present in stratiform, the average thickness of this layer is 25 μm。
Then, pill resistance, appearance and feel are had rated to obtained piloerection shape artificial leather as described below.It will knot Fruit is summarized in table 1.
[pill resistance]
It according to ISO12945-2, is tested using Martindale's abrasion tester, is sentenced by grade benchmark below It is fixed.
5: not changing
4: it can be seen that wildness slightly and/or the ball top being partly formed.
3: it can be seen that moderate wildness and/or moderate pilling, are partially seen test film surface and go out The ball top of existing various sizes and density.
2: the major part on test film surface can be seen apparent wildness and/or apparent pilling, various sizes and The ball top of density.
1: the ball top of intensive wildness and/or very big pilling, various sizes and density coats the entire of test film Surface.
[appearance]
The appearance of the piloerection shape artificial leather to detect by an unaided eye, is determined by benchmark below.
3: the superfine undercoat sense with Niu Bage shape.
2: there is the slightly thick piloerection sense of chamois leather shape or slightly gauffer can be seen on surface.
1: it is significant to there is apparent irregular or gauffer in piloerection length.
[feel]
Obtained piloerection shape artificial leather is bent, determines to compare with piloerection shape natural leather by benchmark below Hardness, the difference of flexibility.
3: being the feel of the balancing good of sense of fulfillment and flexibility close to the feel of piloerection shape natural leather.
2: being comparably harder feel with piloerection shape natural leather.
1: lacking sense of fulfillment compared with piloerection shape natural leather.
Table 1
[embodiment 2]
Use ethylene modified polyvinyl alcohol as the thermoplastic resin of sea component, is made using the PET of isophthalate modified For the thermoplastic resin of island component, melt spinning is carried out to islands-in-sea bicomponent fibre, so that the mass ratio of sea component and island component It for sea component/island component=25/75, and stretched, crispaturaed, cut off, thus obtain fiber number 2.1dtex, average fiber length The staple fiber (staple) of the islands-in-sea bicomponent fibre of 51mm.
Then, using obtained staple fiber, overlay network is respectively prepared with lapper, implements 700 thorns/cm using needing machine2 Needle thorn, obtained weight per unit area 407g/m2Obvolvent net.
Then, using weight per unit area 407g/m such as obtained above2Obvolvent net replace embodiment 1 used in Weight per unit area 415g/m2Obvolvent net in addition to this obtained by method similarly to Example 1 containing a mask There is the piloerection shape artificial leather of the non-woven fabrics in piloerection face.Obtained piloerection shape artificial leather is thickness 0.6mm, weight per unit area 340g/m2, apparent density 0.57g/cm3.In addition, the length of the fiber of fluffing is about 80 μm or so.In addition, the second high score bullet Property body infiltration in fibre plate and adhere to piloerection superfine fibre root, and fibre plate is present in unevenly with stratiform Surface layer, the average thickness of this layer are 25 μm.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[embodiment 3]
In embodiment 1, it is impregnated in such a way that modified PET/solvent system polyurethane mass ratio is 87/13 as second The solvent system polyurethane of macromolecular elastomer is as the first macromolecular elastomer, in embodiment 1, as the first high score bullet Property body, using this replace in embodiment 1 by the lotion of aqueous polyurethane be impregnated in densification after obvolvent net in it is high as first In addition to this molecular flexibility body has been obtained by method similarly to Example 1 containing the nonwoven in one side with piloerection face The piloerection shape artificial leather of cloth.Obtained piloerection shape artificial leather with a thickness of 0.6mm, weight per unit area 350g/m2, apparently Density 0.58g/cm3.In addition, the length of the fiber of fluffing is about 60 μm or so.In addition, the second macromolecular elastomer infiltration in Fibre plate and adhere to piloerection superfine fibre root, be unevenly present in the surface layer of fibre plate with stratiform, this layer it is flat With a thickness of 22 μm.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[embodiment 4]
In embodiment 1, the ratio (solvent by solvent system polyurethane relative to the weight per unit area of aqueous polyurethane System/water system) from 0.012 times be changed to 0.025 times, in addition to this, by method similarly to Example 1 obtained containing The piloerection shape artificial leather of non-woven fabrics with piloerection face on one side.Obtained piloerection shape artificial leather with a thickness of 0.6mm, unit plane Product weight is 350g/m2, apparent density 0.58g/cm3.In addition, the length of the fiber of fluffing is about 40 μm or so.In addition, the Two macromolecular elastomers infiltration in fibre plate and adhere to piloerection superfine fibre root, be unevenly present in stratiform The surface layer of fibre plate, the average thickness of this layer are 35 μm.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[embodiment 5]
In embodiment 1, the ratio (solvent by solvent system polyurethane relative to the weight per unit area of aqueous polyurethane System/water system) from 0.012 times be changed to 0.004 times, in addition to this, by method similarly to Example 1 obtained containing The piloerection shape artificial leather of non-woven fabrics with piloerection face on one side.Obtained piloerection shape artificial leather with a thickness of 0.6mm, unit plane Product weight is 350/m2, apparent density 0.58g/cm3.In addition, the length of the fiber of fluffing is about 180 μm or so.In addition, the Two macromolecular elastomers be impregnated in fibre plate and adhere to piloerection superfine fibre root, be unevenly present in stratiform The surface layer of fibre plate, the average thickness of this layer are 15 μm.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[embodiment 6]
In embodiment 1, the ratio (solvent by solvent system polyurethane relative to the weight per unit area of aqueous polyurethane System/water system) from 0.012 times be changed to 0.0012 times, in addition to this, by method similarly to Example 1 obtained containing The piloerection shape artificial leather of non-woven fabrics with piloerection face on one side.Obtained piloerection shape artificial leather with a thickness of 0.6mm, unit plane Product weight is 350g/m2, apparent density 0.58g/cm3.In addition, the length of the fiber of fluffing is about 300 μm or so.In addition, Second macromolecular elastomer infiltration in fibre plate and adhere to piloerection superfine fibre root, unevenly exist with stratiform In the surface layer of fibre plate, the average thickness of this layer is 10 μm.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[embodiment 7]
In embodiment 1, the ratio (solvent by solvent system polyurethane relative to the weight per unit area of aqueous polyurethane System/water system) from 0.012 times it is changed to 0.05 times, in addition to this, obtained by method similarly to Example 1 containing one Face has the piloerection shape artificial leather of the non-woven fabrics in piloerection face.Obtained piloerection shape artificial leather is with a thickness of 0.6mm, unit area Weight is 355g/m2, apparent density 0.59g/cm3.In addition, the length of the fiber of fluffing is about 20 μm or so.In addition, second Macromolecular elastomer infiltration in fibre plate and adhere to piloerection superfine fibre root, fibre is present in unevenly with stratiform The surface layer of piece is tieed up, the average thickness of this layer is 45 μm.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[comparative example 1]
In addition to this process that coating mixed solvent is omitted in embodiment 1 passes through method same as embodiment 1 The piloerection shape artificial leather containing the non-woven fabrics in one side with piloerection face is obtained.Obtained piloerection shape artificial leather with a thickness of 0.6mm, weight per unit area 350g/m2, apparent density 0.58g/cm3.In addition, the length of the fiber of fluffing is about 20 μm Left and right, but piloerection is uneven and has apparent small gauffer on the surface.In addition, the second macromolecular elastomer adheres to piloerection The top and root of superfine fibre, the surface layer of fibre plate is unevenly present in stratiform, but is not observed to fibre plate The infiltration of thickness direction.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[comparative example 2]
It is coated with the lotion of aqueous polyurethane identical with the substance of the first macromolecular elastomer is used as in embodiment 1 Instead of coating solvent system polyurethane is as the second macromolecular elastomer in embodiment 1, in addition to this, by same with embodiment 1 The method of sample is obtained in piloerection shape artificial leather of the one side containing the non-woven fabrics with piloerection face.Obtained piloerection shape artificial leather With a thickness of 0.6mm, weight per unit area 350g/m2.In addition, the length of the fiber of fluffing is about 300 μm or so.In addition, the Two macromolecular elastomers discontinuously adhere to the top of the superfine fibre of piloerection, and the thickness side to fibre plate is not observed To infiltration.In addition, it can be observed that part falls off in dyeing.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
[comparative example 3]
In embodiment 1, uncoated second macromolecular elastomer and be coated with identical as the substance used in embodiment 1 Mixed solvent, in addition to this, by method similarly to Example 1 obtained containing one side have piloerection face nonwoven The piloerection shape artificial leather of cloth.Obtained piloerection shape artificial leather with a thickness of 0.6mm, weight per unit area 350g/m2.In addition, The length of the fiber of fluffing is about 400 μm or so.
Then, obtained piloerection shape artificial leather is evaluated similarly to Example 1.Show the result in table 1.
The grade benchmark of the pill resistance of piloerection shape artificial leather obtained in Examples 1 to 7 is 4 or more, pill resistance It is high.It should be noted that embodiment 3 has used and has been dissolved in the solvent system polyurethane of solvent as the first macromolecular elastomer, because This, dissolves the first polymer moiety by the coating of solvent, as a result, can see tiny gauffer on surface, becomes slightly Hard feel.In addition, being obtained in the lower embodiment 6 of ratio of solvent system polyurethane/aqueous polyurethane weight per unit area Piloerection shape artificial leather it is weaker to the constraint of the superfine fibre of piloerection, therefore the grade benchmark of pill resistance be 4, it is slightly lower.Separately Outside, piloerection shape people obtained in the higher embodiment 7 of ratio of solvent system polyurethane/aqueous polyurethane weight per unit area The surface of fabricate-leather is slightly hard, as a result, can see tiny gauffer on surface.
On the other hand, the grade benchmark of the pill resistance of the piloerection shape artificial leather of comparative example 1 is 3,1 province of comparative example The process in the mixed solvent of the surface coating dissolution solvent system polyurethane in piloerection face is omited.In addition, the piloerection shape of comparative example 2 The grade benchmark of the appearance of artificial leather is 2, and the comparative example 2 is coated on the surface in piloerection face is not dissolved in solvent Aqueous polyurethane replaces coating solvent system polyurethane.From embodiment 1, the result of comparative example 1 and comparative example 2: in order to improve Pill resistance simultaneously obtains superfine greasy Niu Bage sense, needs to make macromolecular elastomer be dissolved in solvent and permeate in internal layer direction, And make its solidification in the root of superfine fibre.In addition, omitting macromolecular elastomer and being only coated in the comparative example 3 of solvent and obtain To the piloerection length of piloerection shape artificial leather, piloerection sense have it is biggish uneven.
The manufacturing method of the piloerection shape artificial leather explained in detail above has following process: preparing fibre plate Process, the fibre plate contain fiber number 1dtex superfine fibre below and by impregnation impart the first high polymer elastic The non-woven fabrics of body；The process for forming piloerection face and the one or both sides of fibre plate are carried out fluffing processing；It is applied in piloerection face Cloth contains the process to given solvent with the resin liquid of the second soluble macromolecular elastomer；It is being coated with resin liquid Face on be coated with the process of the solvent.According to the manufacturing method of this piloerection shape artificial leather, made pair by the coating of solvent The second macromolecular elastomer dissolution that the surface layer of hair side is assigned and inner layer infiltration are played, it is then solidifying by the volatilization of solvent Gu adhering near the root of the superfine fibre of fluffing.Therefore, superfine by being fluffed with the constraint of the second macromolecular elastomer Fiber, it is also not easy to fall off, it is not easy to protrude from outside even if opposition hair side rubs.As a result, be able to suppress it is so-called Pilling generation, the pilling refers to due to friction surface and superfine fibre is made to fall off, protrude, and then the superfine fibre is mutual The phenomenon that mutually winding and forming block.
In addition, the first macromolecular elastomer for first passing through impregnation in advance to fibre plate and assigning preferably has above-mentioned solvent There is insoluble macromolecular elastomer.In the case where the first macromolecular elastomer is dissolved in solvent, due to solvent imparting and Dissolve the second macromolecular elastomer together with the first macromolecular elastomer, accordingly, there exist the quality of products such as feeling hard hardly possiblies With the tendency of control.
In addition, in the macromolecular elastomer that the first macromolecular elastomer is cross-linked structure to be formed, and the second high score bullet In the case that property body is the macromolecular elastomer for not forming cross-linked structure, for above-mentioned solvent, preferably the first macromolecular elastomer It is difficult to dissolve, the second macromolecular elastomer is easy to dissolve.
As the first macromolecular elastomer, such as preferred aqueous polyurethane, the second macromolecular elastomer is the poly- ammonia of solvent system The balance of ester, the characteristic of thus obtained piloerection shape artificial leather is good, in addition, being typically due to aqueous polyurethane forms crosslinking knot Structure, therefore dissolubility is lower, and since solvent system polyurethane does not form cross-linked structure, dissolubility is higher, examines from this aspect Consider, preferably such case.
In addition, being not easy from the viewpoint of decoherencing from superfine fibre, preferably superfine fibre is long fibre.
In addition, from the viewpoint of never making feel really up to the mark and can be improved pill resistance, preferably the second macromolecular elastomer Weight per unit area be 0.0001~0.05 times of weight per unit area of the first macromolecular elastomer.
In addition, piloerection shape artificial leather contains fibre plate, the fibre plate is embraced fiber number 1dtex superfine fibre below The first macromolecular elastomer is imparted by impregnation in fit non-woven fabrics, fibre plate is in its one or both sides with making pole Piloerection face made of fine fibre fluffing also has the root of the superfine fibre of cementation fluffing and is unevenly present in the fibre Tie up second macromolecular elastomer on the surface layer of piece.The pill resistance of such piloerection shape artificial leather is excellent.
In addition, in the case where the piloerection length of the superfine fibre of fluffing is 30~200 μm, it is natural from that can obtain From the viewpoint of the excellent piloerection shape artificial leather of superfine undercoat sense as Niu Bage shape leather, the preferred situation.
Industrial applicibility
Piloerection shape artificial leather is preferably as tables such as dress material, shoes, furniture, automotive seat, grocery items obtained in the present invention Facestock material uses.

Claims (19)

1. a kind of manufacturing method of piloerection shape artificial leather, this method comprises:
Prepare the process of fibre plate, the fibre plate contains fiber number 1dtex superfine fibre below and imparts by impregnation The non-woven fabrics of first macromolecular elastomer, first macromolecular elastomer are aqueous polyurethane；
The process for forming piloerection face and the one or both sides of the fibre plate are carried out fluffing processing；
Work of the coating containing the solution to given solvent with the second soluble macromolecular elastomer on the piloerection face Sequence, second macromolecular elastomer are solvent system polyurethane；And
The process of the solvent is coated on the face for being coated with the solution.
2. the manufacturing method of piloerection shape artificial leather according to claim 1, wherein first macromolecular elastomer is pair The solvent has insoluble macromolecular elastomer.
3. the manufacturing method of piloerection shape artificial leather according to claim 2, wherein second macromolecular elastomer is to institute The dissolution rate for stating solvent is 90% or more, and first macromolecular elastomer is 10% or less to the dissolution rate of the solvent.
4. the manufacturing method of piloerection shape artificial leather according to claim 2, wherein first macromolecular elastomer be to The macromolecular elastomer of cross-linked structure is formed, second macromolecular elastomer is the high polymer elastic for not forming cross-linked structure Body.
5. the manufacturing method of piloerection shape artificial leather according to claim 1, wherein the superfine fibre is long fibre.
6. the manufacturing method of piloerection shape artificial leather according to claim 1, wherein the list of second macromolecular elastomer Position area weight is 0.001~0.05 times of the weight per unit area of first macromolecular elastomer.
7. a kind of piloerection shape artificial leather, containing fibre plate, the fibre plate is that impart first to non-woven fabrics by impregnation high Fibre plate obtained from molecular flexibility body, the non-woven fabrics be fiber number 1dtex superfine fibre below pseudoconjugant, described first Macromolecular elastomer is aqueous polyurethane,
The fibre plate its one or both sides have so that the superfine fibre is fluffed made of piloerection face, also having will fluff The root cementation of the superfine fibre and the second macromolecular elastomer for permeating and being non-uniformly distributed in the fibre plate surface layer, Second macromolecular elastomer is solvent system polyurethane, and the piloerection length of the superfine fibre of fluffing is 20~200 μm.
8. piloerection shape artificial leather according to claim 7, wherein first macromolecular elastomer has given solvent Have it is insoluble, second macromolecular elastomer to the solvent have solubility.
9. piloerection shape artificial leather according to claim 8, wherein second macromolecular elastomer is to the molten of the solvent Solution rate is 90% or more, and first macromolecular elastomer is 10% or less to the dissolution rate of the solvent.
10. piloerection shape artificial leather according to claim 7, wherein the aqueous polyurethane has cross-linked structure, described molten Agent system polyurethane does not have cross-linked structure.
11. piloerection shape artificial leather according to claim 7, wherein second macromolecular elastomer is with stratiform or membranaceous Infiltration and the surface layer for being unevenly present in the fibre plate, the average thickness in the region are 5~60 μm.
12. piloerection shape artificial leather according to claim 7, wherein the superfine fibre is long fibre.
13. piloerection shape artificial leather according to claim 7, wherein the unit area weight of second macromolecular elastomer Amount is 0.001~0.05 times of the weight per unit area of first macromolecular elastomer.
14. a kind of piloerection shape artificial leather, containing fibre plate, the fibre plate is that impart first to non-woven fabrics by impregnation high Fibre plate obtained from molecular flexibility body, the non-woven fabrics be fiber number 1dtex superfine fibre below pseudoconjugant, described first Macromolecular elastomer is aqueous polyurethane,
In its one or both sides with superfine fibre fluffing piloerection face made of is made, also having will fluff the fibre plate The superfine fibre root cementation and be non-uniformly distributed in second macromolecular elastomer on the fibre plate surface layer, it is described Second macromolecular elastomer is solvent system polyurethane,
Second macromolecular elastomer is with stratiform or the membranaceous surface layer permeated and be unevenly present in the fibre plate, the area The average thickness in domain is 5~60 μm.
15. piloerection shape artificial leather according to claim 14, wherein first macromolecular elastomer is to given solvent With insoluble, second macromolecular elastomer has solubility to the solvent.
16. piloerection shape artificial leather according to claim 15, wherein second macromolecular elastomer is to the solvent Dissolution rate is 90% or more, and first macromolecular elastomer is 10% or less to the dissolution rate of the solvent.
17. piloerection shape artificial leather according to claim 14, wherein the aqueous polyurethane has cross-linked structure, described Solvent system polyurethane does not have cross-linked structure.
18. piloerection shape artificial leather according to claim 14, wherein the superfine fibre is long fibre.
19. piloerection shape artificial leather according to claim 14, wherein the unit area weight of second macromolecular elastomer Amount is 0.001~0.05 times of the weight per unit area of first macromolecular elastomer.
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